JP2915509B2 - Method for molding acrylonitrile-based resin container - Google Patents
Method for molding acrylonitrile-based resin containerInfo
- Publication number
- JP2915509B2 JP2915509B2 JP2177786A JP17778690A JP2915509B2 JP 2915509 B2 JP2915509 B2 JP 2915509B2 JP 2177786 A JP2177786 A JP 2177786A JP 17778690 A JP17778690 A JP 17778690A JP 2915509 B2 JP2915509 B2 JP 2915509B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylonitrile
- preform
- based resin
- molding
- resin container
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims description 53
- 229920005989 resin Polymers 0.000 title claims description 44
- 239000011347 resin Substances 0.000 title claims description 44
- 238000000034 method Methods 0.000 title claims description 12
- 238000000465 moulding Methods 0.000 title claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- 238000000071 blow moulding Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000010894 electron beam technology Methods 0.000 claims description 16
- 150000001869 cobalt compounds Chemical class 0.000 claims description 11
- -1 formaldehyde compound Chemical class 0.000 claims description 7
- 231100000987 absorbed dose Toxicity 0.000 claims description 2
- 230000006698 induction Effects 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229920001893 acrylonitrile styrene Polymers 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- KDMCQAXHWIEEDE-UHFFFAOYSA-L cobalt(2+);7,7-dimethyloctanoate Chemical compound [Co+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O KDMCQAXHWIEEDE-UHFFFAOYSA-L 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/42—Component parts, details or accessories; Auxiliary operations
- B29C49/78—Measuring, controlling or regulating
- B29C49/786—Temperature
- B29C2049/7861—Temperature of the preform
- B29C2049/7862—Temperature of the preform characterised by temperature values or ranges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/18—Polymers of nitriles
- B29K2033/20—PAN, i.e. polyacrylonitrile
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、アクリロニトリル系樹脂容器の成形方法で
あって、二軸延伸ブロー成形法によるアクリロニトリル
系樹脂容器中の未重合アクリロニトリル単量体及び二軸
延伸ブロー成形法で溶出するHCNを低減した二軸延伸ブ
ロー成形法によるアクリロニトリル系樹脂容器の成形方
法を提供することにある。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for molding an acrylonitrile-based resin container, comprising an unpolymerized acrylonitrile monomer and a acrylonitrile-based monomer in an acrylonitrile-based resin container by a biaxial stretch blow molding method. An object of the present invention is to provide a method for molding an acrylonitrile-based resin container by a biaxial stretch blow molding method in which HCN eluted by an axial stretch blow molding method is reduced.
［従来の技術］ アクリロニトリル系樹脂の有底筒状体（以下プリフォ
ームという）を二軸延伸ブロー成形法で製造するアクリ
ロニトリル系樹脂容器は、ガスバリヤー性と透明性とに
おいて優れた性質を有するものであり、しかも軽量で、
かつ多くの溶剤に対して優れた安定性をも具備するもの
であるため、各種容器、例えば食品、薬品、化粧品、炭
酸ガス含有飲料品充填用等の容器として広く利用されて
いる。[Prior Art] An acrylonitrile-based resin container for producing a bottomed cylindrical body (hereinafter referred to as a preform) of an acrylonitrile-based resin by a biaxial stretch blow molding method has excellent properties in gas barrier properties and transparency. And lightweight,
Further, since it has excellent stability to many solvents, it is widely used as various containers, for example, containers for filling foods, medicines, cosmetics, and beverages containing carbon dioxide gas.
しかしながら、前記アクリロニトリル系樹脂の二軸延
伸ブロー成形法の容器は、原料であるアクリロニトリル
系樹脂自体に痕跡量の未重合のアクリロニトリル単量体
が含有されており、また容器の射出成形時に痕跡量の未
重合のアクリロニトリル単量体が生成され、必然的にこ
れらが前記二軸延伸ブロー成形法の容器に含有され、こ
れが容器の内容物に移行する可能性を有している。However, the container of the acrylonitrile-based resin biaxial stretch blow molding method contains a trace amount of unpolymerized acrylonitrile monomer in the raw material acrylonitrile-based resin itself, and also has a trace amount during injection molding of the container. Unpolymerized acrylonitrile monomers are produced, which are inevitably contained in the container of the biaxial stretch blow molding method, and have a possibility of transferring to the contents of the container.
このため、例えば特公昭56−54321号公報又は特開昭5
4−148059号公報に記載されているように、アクリロニ
トリル系樹脂を主成分とする熱可塑性樹脂のプリフォー
ムに電子ビームを照射することによって、該プリフォー
ム中における未重合のアクリロニトリル単量体の含有量
を低減させる方法が提案されている。For this reason, for example, Japanese Patent Publication No.
As described in JP-A-4-148059, by irradiating an electron beam to a preform of a thermoplastic resin containing an acrylonitrile-based resin as a main component, the prepolymer contains unpolymerized acrylonitrile monomer. Methods for reducing the amount have been proposed.
［本発明が解決しようとする課題］ 処で、前記アクリロニトリル系樹脂のプリフォームに
電子ビームを照射することによって該プリフォーム中の
未重合のアクリロニトリル単量体の含有量を低減させる
方法は、電子ビームの照射によってHCNが副生されると
いう別の問題を有しており、アクリロニトリル系樹脂に
よる優れた衛生特性を有する延伸ブロー成形法による容
器、特に小型容器は依然として得られないのが実情であ
る。[Problems to be Solved by the Invention] A method for reducing the content of unpolymerized acrylonitrile monomer in the preform by irradiating the preform of the acrylonitrile-based resin with an electron beam is disclosed in There is another problem that HCN is by-produced by beam irradiation, and in fact, containers by stretch blow molding method having excellent sanitary properties by acrylonitrile-based resin, especially small containers are still not available. .
本発明は、かかる現状に鑑み、二軸延伸ブロー成形法
によるアクリロニトリル系樹脂容器の製造に当たり、プ
リフォーム中の未重合のアクリロニトリル単量体の含有
量と、副生するHCNの生成量とを、共に極めて少量に低
減させ、得かつ衛生特性に優れた二軸延伸ブロー成形法
によるアクリロニトリル系樹脂容器を製造する方法を提
供するものである。The present invention, in view of the current situation, upon producing an acrylonitrile-based resin container by the biaxial stretch blow molding method, the content of the unpolymerized acrylonitrile monomer in the preform, and the amount of HCN produced as a by-product, An object of the present invention is to provide a method for producing an acrylonitrile-based resin container by a biaxial stretch blow molding method which is reduced to a very small amount and which is excellent in hygiene properties.
［課題を解決するための手段］ 本発明は、アクリロニトリル系樹脂に、ホルムアルデ
ヒド化合物及びコバルト化合物を添加してプリフォーム
に成形し、これに低い吸収線量の電子ビームを照射した
後、直ちに40℃以上の温度で加熱処理を施すという構成
のものである。[Means for Solving the Problems] The present invention provides a acrylonitrile-based resin to which a formaldehyde compound and a cobalt compound are added to form a preform, which is irradiated with an electron beam having a low absorption dose, and then immediately heated to 40 ° C. or higher. The heat treatment is performed at this temperature.
［作用］ 本発明は以上の如き構成からなるものであって、アク
リロニトリル系樹脂のプリフォーム中に、ホルムアルデ
ヒド化合物及びコバルト化合物を添加すること、該プリ
フォームに低い吸収線量の電子ビームを照射すること及
びその後直ちに40℃以上の加熱処理を施すという構成に
よってこれらの効果が夫々相乗され、プリフォーム中の
未重合のアクリロニトリル単量体を0.1ppm以下に抑える
ことができると共に、二軸延伸ブロー成形中に副生され
るHCNの量を溶出試験浸出用液基準で15ppb以下と低くさ
れた二軸延伸ブロー成形法によるアクリロニトリル系樹
脂容器を得ることができる。[Function] The present invention is configured as described above, and comprises adding a formaldehyde compound and a cobalt compound to a preform of an acrylonitrile-based resin, and irradiating the preform with an electron beam having a low absorption dose. These effects are respectively synergized by a configuration in which a heat treatment of 40 ° C. or more is performed immediately thereafter, and the unpolymerized acrylonitrile monomer in the preform can be suppressed to 0.1 ppm or less, and during the biaxial stretch blow molding. An acrylonitrile-based resin container can be obtained by a biaxial stretch blow molding method in which the amount of HCN produced as a by-product is reduced to 15 ppb or less based on the leaching solution for the dissolution test.
本発明で使用するホルムアルデヒド化合物としては、
パラトルエンスルホン酸アミド・ホルムアルデヒド重縮
合物であって、重合体に対するホルムアルデヒド化合物
の量はアクリロニトリル系樹脂に対する重量基準で0.15
％以下とする。0.15％を超えるとポジテイブリストの制
限をオーバーするため好ましくない。As the formaldehyde compound used in the present invention,
Paratoluenesulfonic acid amide-formaldehyde polycondensate, wherein the amount of the formaldehyde compound relative to the polymer is 0.15 based on the weight of the acrylonitrile resin.
% Or less. If it exceeds 0.15%, it is not preferable because it exceeds the limit of the positive list.
本発明で使用するコバルト化合物としては、酢酸コバ
ルト４水和物、ステアリン酸コバルト、ネオデカン酸コ
バルト、ナフテン酸コバルト等が挙げられる。Examples of the cobalt compound used in the present invention include cobalt acetate tetrahydrate, cobalt stearate, cobalt neodecanoate, and cobalt naphthenate.
更に、プリフォームがコバルト化合物を含有している
場合には、得られる容器がコバルト化合物を含んでいな
い場合の容器よりも酸素遮断性が高く、またコバルト化
合物の添加量に対する酸素遮断性の効果は、添加量に比
例して増大する。Furthermore, when the preform contains a cobalt compound, the resulting container has a higher oxygen barrier property than the case where the cobalt compound is not contained, and the effect of the oxygen barrier property on the added amount of the cobalt compound is , Increases in proportion to the amount added.
他方、前記プリフォーム中にコバルト化合物を多く含
んでいる場合には二軸延伸ブロー成形法によって得られ
る樹脂容器が褐色となり、色相に影響を及ぼすこととな
る。On the other hand, when the preform contains a large amount of the cobalt compound, the resin container obtained by the biaxial stretch blow molding method becomes brown, which affects the hue.
従って、プリフォーム中に添加されるコバルト化合物
は前記色相、二軸延伸ブロー成形中に副生するHCNの量
の低減、或は酸素遮断性等を考慮すると、プリフォーム
中に添加されるコバルト化合物の量は、重合体に対する
コバルトの重量基準で200ppm以下、好ましくは50〜100p
pmの範囲が有効である。Therefore, considering the hue, the amount of HCN by-produced during biaxial stretch blow molding, or the oxygen barrier properties, etc., the cobalt compound added to the preform is added to the preform. Is 200 ppm or less based on the weight of cobalt relative to the polymer, preferably 50-100 p
The pm range is valid.
更に、本発明における電子ビームの照射は、プリフォ
ーム中の未重合のアクリロニトリル単量体の重合を図る
と共に、前記プリフォームの二軸延伸ブロー成形中に副
生するHCNの量をできるだけ少量に抑えるものであるか
ら、プリフォームへの電子ビームの吸収線量は、例えば
0.1〜8.0キログレイの如く低線量を使用する。従って、
プリフォームの平均肉厚は10〜80mm程度とし、電子ビー
ムがプリフォーム内部まで充分に照射できるようにする
必要がある。Further, the irradiation of the electron beam in the present invention aims at polymerization of the unpolymerized acrylonitrile monomer in the preform and suppresses the amount of HCN by-produced during the biaxial stretch blow molding of the preform as small as possible. Therefore, the absorbed dose of the electron beam to the preform is, for example,
Use low doses, such as 0.1-8.0 kilogray. Therefore,
The average thickness of the preform must be about 10 to 80 mm so that the electron beam can be sufficiently irradiated inside the preform.
更に、電子ビーム照射後直ちに40℃以上の温度による
加熱処理は未重合のアクリロニトリル単量体の重合を促
進することができるもので、この場合の加熱処理は熱風
加熱、高周波加熱、誘導加熱、遠赤外線加熱、近赤外線
加熱或はこれらの加熱手段の２以上の組み合わせ等何れ
の手段によっても良い。Furthermore, heat treatment at a temperature of 40 ° C. or higher immediately after electron beam irradiation can promote the polymerization of unpolymerized acrylonitrile monomer. In this case, the heat treatment is hot air heating, high-frequency heating, induction heating, and remote heating. Any means such as infrared heating, near infrared heating, or a combination of two or more of these heating means may be used.
本発明で使用されるアクリロニトリル系樹脂はアクリ
ロニトリルとして計算されるニトリル単量体が55〜85重
量％程度含んでいるものが利用される。また、二軸延伸
ブロー成形に付すプリフォームは一般のプリフォームと
同一構造のものが利用できる。As the acrylonitrile resin used in the present invention, a resin containing about 55 to 85% by weight of a nitrile monomer calculated as acrylonitrile is used. As the preform to be subjected to biaxial stretch blow molding, a preform having the same structure as a general preform can be used.
尚、本発明の容器は包装容器としての味覚性に悪影響
を及ぼさない程度に熱安定剤、染料、顔料、可塑剤、酸
化防止剤、潤滑剤等の各種添加剤を使用できることは勿
論である。The container of the present invention can of course use various additives such as a heat stabilizer, a dye, a pigment, a plasticizer, an antioxidant, and a lubricant to such an extent that the taste of the packaging container is not adversely affected.
［実 施 例］ 以下実施例をもって本発明を具体的に説明する。[Examples] The present invention will be specifically described below with reference to examples.
実施例１ アクリロニトリル−スチレン共重合体（アクリロニト
リル単量体成分70重量％）100重量部、パラトルエンス
ルホン酸アミド・ホルムアルデヒド樹脂0.15重量部、酢
酸コバルト４水和物50ppmからなる樹脂混合物を成形用
原料とする射出成形によって長さ約220mm、平均壁厚約
4.8mmのプリフォームを成形した。尚、このプリフォー
ム中の未重合のアクリロニトリル単量体の量は9.0ppmで
あった。Example 1 A resin mixture comprising 100 parts by weight of an acrylonitrile-styrene copolymer (70% by weight of an acrylonitrile monomer component), 0.15 parts by weight of paratoluenesulfonic acid amide / formaldehyde resin, and 50 ppm of cobalt acetate tetrahydrate was used as a raw material for molding. By injection molding, length is about 220mm, average wall thickness is about
A 4.8 mm preform was molded. The amount of the unpolymerized acrylonitrile monomer in this preform was 9.0 ppm.
次いで、前記プリフォームの長軸を軸として回転させ
ながら、該プリフォームに3MeVの加速電圧の電子線照射
装置で５キログレイの電子線を照射し、該照射処理に続
き、直ちに90℃の熱風にて30分間加熱処理を施した。Next, the preform was irradiated with an electron beam of 5 kilogray using an electron beam irradiation device having an acceleration voltage of 3 MeV while rotating about the major axis of the preform. Immediately after the irradiation treatment, the preform was heated to 90 ° C. hot air. For 30 minutes.
しかる後、前記処理後のプリフォームを二軸延伸ブロ
ー成形に付し、容量1500mlの容器［Ｉ］を得た。Thereafter, the treated preform was subjected to biaxial stretch blow molding to obtain a container [I] having a capacity of 1500 ml.
実施例２ アクリロニトリル−スチレン共重合体（アクリロニト
リル単量体成分70重量％）100重量部、パラトルエンス
ルホン酸アミド・ホルムアルデヒド樹脂0.15重量部、酢
酸コバルト４水和物100ppmからなる樹脂混合物を射出成
形によって長さ約220mm、平均壁厚約4.8mmのプリフォー
ムを成形した。該プリフォーム中の未重合のアクリロニ
トリル単量体の量は9.5ppmであった。Example 2 A resin mixture consisting of 100 parts by weight of an acrylonitrile-styrene copolymer (70% by weight of an acrylonitrile monomer component), 0.15 parts by weight of paratoluenesulfonic acid amide / formaldehyde resin, and 100 ppm of cobalt acetate tetrahydrate was subjected to injection molding. A preform having a length of about 220 mm and an average wall thickness of about 4.8 mm was formed. The amount of unpolymerized acrylonitrile monomer in the preform was 9.5 ppm.
次いで、前記プリフォームの長軸を軸として回転させ
ながら、該プリフォームに実施例１と同様な電子線照射
装置で同様に５キログレイの電子線を照射し、その後直
ちに90℃の熱風で30分間加熱処理を施した。Next, the preform was irradiated with an electron beam of 5 kg gray in the same manner using the same electron beam irradiation apparatus as in Example 1 while rotating about the major axis of the preform, and immediately thereafter, heated with 90 ° C. hot air for 30 minutes. Heat treatment was performed.
しかる後、前記処理後のプリフォームを二軸延伸ブロ
ー成形に付し、容量1500mlの容器［II］を得た。Thereafter, the treated preform was subjected to biaxial stretch blow molding to obtain a container [II] having a capacity of 1500 ml.
実施例３ アクリロニトリル−スチレン共重合体（アクリロニト
リル単量体成分70重量％）100重量部、パラトルエンス
ルホン酸アミド・ホルムアルデヒド樹脂0.15重量部、酢
酸コバルト４水和物200ppmからなる樹脂混合物を射出成
形によって長さ約220mm、平均壁厚約4.8mmのアクリロニ
トリル系樹脂のプリフォームを成形した。該プリフォー
ム中の未重合のアクリロニトリル単量体の量は9.7ppmで
あった。Example 3 A resin mixture consisting of 100 parts by weight of an acrylonitrile-styrene copolymer (70% by weight of an acrylonitrile monomer component), 0.15 part by weight of a paratoluenesulfonic acid amide / formaldehyde resin, and 200 ppm of cobalt acetate tetrahydrate was subjected to injection molding. An acrylonitrile resin preform having a length of about 220 mm and an average wall thickness of about 4.8 mm was molded. The amount of unpolymerized acrylonitrile monomer in the preform was 9.7 ppm.
次いで、前記プリフォームの長軸を軸として回転させ
ながら、該プリフォームに実施例１と同一の電子線照射
装置で同様に５キログレイの電子線を照射し、その後直
ちに90℃の熱風で30分間加熱処理を施した。Next, the preform was irradiated with a 5 kg gray electron beam in the same manner as in Example 1 while rotating about the major axis of the preform, and immediately thereafter, heated with 90 ° C. hot air for 30 minutes. Heat treatment was performed.
しかる後、前記プリフォームを二軸延伸ブロー成形に
付し、容量1500mlの容器［III］を得た。Thereafter, the preform was subjected to biaxial stretching blow molding to obtain a container [III] having a capacity of 1500 ml.
比較例 アクリロニトリル−スチレン共重合体（アクリロニト
リル単量体70重量％）100重量部、パラトルエンスルホ
ン酸アミド・ホルムアルデヒド樹脂0.15重量部からなる
樹脂混合物を射出成形によって長さ約220mm、平均壁厚
約4.8mmのアクリロニトリル系樹脂のプリフォームを成
形した。該プリフォーム中の未重合のアクリロニトリル
単量体の量は8.8ppmであった。Comparative Example A resin mixture consisting of 100 parts by weight of an acrylonitrile-styrene copolymer (70% by weight of an acrylonitrile monomer) and 0.15 part by weight of a paratoluenesulfonic acid amide / formaldehyde resin was injection molded to a length of about 220 mm and an average wall thickness of about 4.8. A preform of acrylonitrile resin having a thickness of mm was molded. The amount of unpolymerized acrylonitrile monomer in the preform was 8.8 ppm.
次いで、前記各実施例と同様に前記プリフォームに電
子線を照射し、その後直ちに90℃の熱風で30分間加熱処
理を施した。Next, the preform was irradiated with an electron beam in the same manner as in each of the above Examples, and immediately thereafter, a heat treatment was performed with hot air at 90 ° C. for 30 minutes.
しかる後、前記プリフォームを二軸延伸ブロー成形に
付し、容量1500mlの容器［IV］を得た。Thereafter, the preform was subjected to biaxial stretch blow molding to obtain a container [IV] having a capacity of 1500 ml.
以上の実施例１〜３及び比較例で得られた容器［Ｉ］
〜［IV］の材質中のアクリロニトリル単量体の量、シア
ンイオンの抽出量、酸素遮断性（O2透過量）を下記表−
１に示す。Containers [I] obtained in the above Examples 1 to 3 and Comparative Example
The amount of acrylonitrile monomer in the material of the ~ [IV], the extracted amount of cyanide ion, Table oxygen barrier properties (O 2 permeation amount) -
It is shown in FIG.
尚、実施例及び比較例におけるシアンイオンの溶出量
は、８％アルコール液からなる溶出試験浸出用液を40℃
に加熱し、これを各容器の規定の入目線の位置まで充填
し密栓後、40℃の雰囲気中に10日間放置することによっ
て溶出されたシアンイオンの量である。The amount of cyan ion eluted in Examples and Comparative Examples was as follows.
This is the amount of cyanide ion eluted by filling each container up to the specified line of sight, sealing it, and leaving it in an atmosphere at 40 ° C. for 10 days.
更に、ここで、溶出されたシアンイオンの試験方法
は、JIS K−0102によるものであり、また、『40℃×10
日間』の保存条件は、30℃以下の数カ月間におよぶ食品
の容器包装用合成樹脂位に対し、西欧諸国で適用されて
いる法的基準である。Furthermore, the test method of the eluted cyan ion here is based on JIS K-0102, and “40 ° C. × 10
The storage condition of “days” is a legal standard applied in Western European countries for synthetic resins for food containers and packaging for several months at 30 ° C or less.
［発明の効果］ 以上の如く本発明は、二軸延伸ブロー成形法によるア
クリロニトリル系樹脂容器の成形法において、プリフォ
ーム中に、予じめホルムアルデヒド化合物及びコバルト
化合物を添加すること、該プリフォームに弱い電子ビー
ムを照射すること及びその後直ちに40℃以上の温度で加
熱処理するという手段により、これらの効果が夫々相乗
されて未重合のアクリロニトリル単量体を重合させて、
該アクリロニトリル単量体の量を0.1ppm以下とし、同時
に二軸延伸ブロー成形法の際副生するHCNの溶出量を15p
pb以下に抑えることができる。 [Effects of the Invention] As described above, the present invention relates to a method for molding an acrylonitrile-based resin container by a biaxial stretch blow molding method, wherein a formaldehyde compound and a cobalt compound are added to a preform in advance, and the preform is added to the preform. By irradiating a weak electron beam and immediately thereafter heating at a temperature of 40 ° C. or higher, these effects are respectively synergized to polymerize the unpolymerized acrylonitrile monomer,
The amount of the acrylonitrile monomer is set to 0.1 ppm or less, and the elution amount of HCN by-produced during the biaxial stretch blow molding method is reduced by 15 p.
pb or less.
従って、本発明の二軸延伸ブロー成形法で得られたア
クリロニトリル系樹脂容器は、従来の二軸延伸ブロー成
形法で得られる樹脂容器と同様に、ガスバリヤー性と透
明性に優れた性質を有し、しかも軽量で、かつ多くの溶
剤に対して優れた安定性をも具備するものであることは
勿論のこと、未重合のアクリロニトリル単量体の量が0.
1ppm以下で、また二軸延伸ブロー成形法で副生されるHC
Nの溶出量が15ppb以下の衛生特性に優れた容器であるか
ら、食品、薬品、化粧品、炭酸ガス含有飲料等を充填す
るための容器として極めて優れた容器を提供するという
効果を奏することができる。Therefore, the acrylonitrile-based resin container obtained by the biaxial stretch blow molding method of the present invention has properties excellent in gas barrier properties and transparency similarly to the resin container obtained by the conventional biaxial stretch blow molding method. And, of course, it is lightweight and has excellent stability against many solvents, and the amount of unpolymerized acrylonitrile monomer is 0.
HC at 1 ppm or less and by-produced by biaxial stretch blow molding
Since it is a container having excellent sanitary properties with an elution amount of N of 15 ppb or less, an effect of providing an extremely excellent container as a container for filling food, medicine, cosmetics, a beverage containing carbon dioxide, etc. can be exerted. .
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｋ 5/09 Ｃ０８Ｋ 5/09 Ｃ０８Ｌ 33/20 Ｃ０８Ｌ 33/20 // Ｂ２９Ｂ 13/08 Ｂ２９Ｂ 13/08 Ｂ２９Ｋ 33:20 Ｂ２９Ｌ 22:00 (58)調査した分野(Int.Cl.6，ＤＢ名) B29C 49/00 - 49/80 B29B 11/00 - 11/16 B29B 13/00 - 13/08 C08L 33/20 C08F 20/44 C08J 3/28 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C08K 5/09 C08K 5/09 C08L 33/20 C08L 33/20 // B29B 13/08 B29B 13/08 B29K 33:20 B29L 22 : 00 (58) Field surveyed (Int.Cl. 6 , DB name) B29C 49/00-49/80 B29B 11/00-11/16 B29B 13/00-13/08 C08L 33/20 C08F 20/44 C08J 3/28
Claims (6)
デヒド化合物及びコバルト化合物を添加して有底筒状体
からなるプリフォームに成形し、これに低い吸収線量の
電子ビームを照射した後、直ちに40℃以上の温度で加熱
処理を施し、次いで前記プリフォームを二軸延伸ブロー
成形することを特徴とするアクリロニトリル系樹脂容器
の成形方法。An acrylonitrile-based resin is added with a formaldehyde compound and a cobalt compound to form a preform formed of a cylindrical body having a bottom. A method for forming an acrylonitrile-based resin container, comprising subjecting the preform to a heat treatment at the above temperature and then biaxially stretch-blow-molding the preform.
を、該樹脂に対する重量基準で200ppm以下で添加するこ
とを特徴とする特許請求の範囲第１項記載のアクリロニ
トリル系樹脂容器の成形方法。2. The method for molding an acrylonitrile-based resin container according to claim 1, wherein a cobalt compound is added to the acrylonitrile-based resin in an amount of 200 ppm or less based on the weight of the resin.
ド化合物を該樹脂に対する重量基準で0.15％以下で添加
することを特徴とする特許請求の範囲第１項記載のアク
リロニトリル系樹脂容器の成形方法。3. The method for molding an acrylonitrile-based resin container according to claim 1, wherein a formaldehyde compound is added to the acrylonitrile-based resin in an amount of 0.15% or less based on the weight of the resin.
レイである特許請求の範囲第１項記載のアクリロニトリ
ル系樹脂容器の成形方法。4. The method for molding an acrylonitrile-based resin container according to claim 1, wherein the absorbed dose of the electron beam is 0.1 to 8 kilogray.
る特許請求の範囲第１項記載のアクリロニトリル系樹脂
容器の成形方法。5. The method for molding an acrylonitrile-based resin container according to claim 1, wherein the preform has an average thickness of 10 to 80 mm.
高周波加熱、誘導加熱、遠赤外線加熱、近赤外線加熱又
はこれらの加熱手段の少なくとも２以上の組み合わせに
よる加熱処理を施すことを特徴とする特許請求の範囲第
１項、第２項、第３項又は第４項記載のアクリロニトリ
ル系樹脂容器の成形方法。6. The heat treatment at a temperature of 40 ° C. or more is performed by hot air heating,
The heat treatment by high frequency heating, induction heating, far-infrared heating, near-infrared heating or a combination of at least two or more of these heating means. The method for molding an acrylonitrile-based resin container according to claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2177786A JP2915509B2 (en) | 1990-07-05 | 1990-07-05 | Method for molding acrylonitrile-based resin container |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2177786A JP2915509B2 (en) | 1990-07-05 | 1990-07-05 | Method for molding acrylonitrile-based resin container |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0464427A JPH0464427A (en) | 1992-02-28 |
| JP2915509B2 true JP2915509B2 (en) | 1999-07-05 |
Family
ID=16037081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2177786A Expired - Fee Related JP2915509B2 (en) | 1990-07-05 | 1990-07-05 | Method for molding acrylonitrile-based resin container |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2915509B2 (en) |
-
1990
- 1990-07-05 JP JP2177786A patent/JP2915509B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0464427A (en) | 1992-02-28 |
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